Thermal Analysis of Materials Group-6

Hamzah Mukhtar Pablo Ramos Vamakshi Khati Daniel Gomez

Contents
PROBLEM

INTRODUCTION TO PRODUCT
DSC DILATOMETRY DMTA CONCLUSION SUMMARY REFERNCES

Problem
One Asian customer has a problem with a polymer gland that fails after a few months. It is observed that this polymer has multiple fractures and its surface is a bit harder than the reference sample. This polymer cable gland is used in power cable. There are several factors that are to be considered for failure of a material.

Introduction to Product
Polymer cable glands attaches and holds the end of a

cable to the equipment. Polymer properties specifically depends on some specific parameters like Tg, Tm, temperature of crystallisation, degree of crystallinity and degradation. So to estimate why the polymer becomes harder and fractures we have to analyse the characteristics of polymers using DSC, DMTA and Dilatometry.

Differential Scanning Calorimetry (DSC)

DSC stands for differential scanning calorimetry is a

thermo-analytical technique. It measures the amount of heat absorbed or released when a sample is cooled or heated and thus providing the data that is related with them. DSC chambers consist of two more or less equal chambers one chamber contains the inert reference sample (usually alumina) where the heat capacitance is well defined in more or less all temperature ranges and in the other chamber is our sample.

Schematic diagram of a typical differential scanning calorimeter.

 DSC determines the thermal transitions in polymers, by

which we can understand the behaviour of our polymer cable gland and to compare it with our reference sample. The information thus collected can determine the changes in the polymer. The following diagram shows some changes in our material and they are showed in endothermic/exothermic reactions.

Dilatometry
It is the thermo-analytical method which is used for the

measurement of shrinkage and expansion of the materials under controlled temperature range. The amount of shrinkage or expansion is dependent on material properties or characteristics. By using dilatometry following properties can be measured Thermal expansion and coefficient of thermal expansion Volumetric expansion Influence of additives/raw materials Density change Glass transition temperature (Tg) Dilatometric softening point (Td) Phase transition

Pushrod dilatometry is a method that is used for determination of dimensional changes versus temperature or time while sample is subjected to a controlled temperature program.

L0=Initial sample length T=Change in temperature

Dynamic Mechanical Thermal Analysis

DMTA or DMA measures the temperature dependent visco-

elastic properties along with modulus of elasticity. Strain is measured by applying fluctuating stress and thus complex modulus is determined. This approach can be used to locate the Tg of the material, as well as to identify transitions corresponding to other molecular motions. Temperature-sweeping DMA is often used to characterize the glass transition te DMA measures the visco-elastic properties by transient or dynamic oscillatory tests temperature of a material.

 Transient tests include stress relaxation and creep. In

dynamic oscillatory test, a sinusoidal stress is applied and sinusoidal strain is measured along with phase difference. For polymers the phase difference is intermediate as in next figure.

Polymer Description
In Asia region these glands used for power cables are made of

polymers with high content in halogens (for instance PVC can reach 57% of chloride), this is also a problem because it could lead to degradation of the polymer easily. Degradation can occur as a result of the formation and then breakage of double bonds (for instance when a Carbon is bond with a halogen and it breaks). This occurs in PVC in the presence of an acid species. Active Hydrogen atoms will remove a Chlorine atom from the polymer molecule, forming Hydrochloric acid (HCl) causing de-chlorination of adjacent Carbon atoms. These de-chlorinated Carbon atoms tend to form double bonds which can be broken in an ozone atmosphere (normal conditions).

Conclusion
Some mechanisms of hardening are related with

recrystallization, as they will increase the percentage of crystallinity of the polymer. As a result it will get harder, and get brittle, which along with stresses could lead to failure. Introducing oxygen and carbon atoms in the main chain will lead to hardening, besides C-C bonds, oxygen atoms are introduced generating a dipole. The link will be reinforced so there will be an increase in resistance to being deformed, so atmospheric conditions should also be taken into account.

 Conclusions are related then to avoid recrystallization

(be aware of Tg and temperature of recrystallization of the polymer), take into account atmosphere conditions and content of halogens in the polymer used.

Summary
Introduction to polymer glands

Discussed about the Problem to the

product Methods being used to Analyse the Problem

References

http://en.wikipedia.org/wiki/Differential_scanning_c alorimetry http://en.wikipedia.org/wiki/Differential_thermal_an alysis http://www.pslc.ws/macrog/dsc.htm http://www.mate.tue.nl/mate/pdfs/10367.pdf http://en.wikipedia.org/wiki/Dynamic_mechanical_a nalysis http://en.wikipedia.org/wiki/Polyvinyl_chloride http://www.files.chem.vt.edu/chemdept/marand/Lecture23.pdf